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EP0566480A1 - Sonde de mesure à membrane à perméabilite sélective et son procédé de fabrication - Google Patents

Sonde de mesure à membrane à perméabilite sélective et son procédé de fabrication Download PDF

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Publication number
EP0566480A1
EP0566480A1 EP93400962A EP93400962A EP0566480A1 EP 0566480 A1 EP0566480 A1 EP 0566480A1 EP 93400962 A EP93400962 A EP 93400962A EP 93400962 A EP93400962 A EP 93400962A EP 0566480 A1 EP0566480 A1 EP 0566480A1
Authority
EP
European Patent Office
Prior art keywords
elongated element
colored indicator
membrane
tube
medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP93400962A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jean Bienvenu
Gil Michard
Jean-Pierre Ciabrini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0566480A1 publication Critical patent/EP0566480A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N2021/0346—Capillary cells; Microcells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N2021/7706—Reagent provision
    • G01N2021/7733—Reservoir, liquid reagent

Definitions

  • the present invention relates to a measurement cell containing a colored indicator solution intended to be immersed in a medium with which it can react by an ion transfer or by a gas transfer through a membrane with selective permeability and its manufacturing process.
  • the present invention is more particularly suitable for measuring the concentration of carbon dioxide or carbon dioxide, dissolved in sea water. It seems particularly advantageous, in an environment subject to pollution of industrial origin, to be able to predict the evolution over time of the concentration of gases favoring the greenhouse effect, and in particular carbon dioxide.
  • the measurement cell belongs to the category of so-called "active" measurement cells because it includes an appropriate reagent which, under the effect of the transfer to be studied, interacts with incident light. Studying the light resulting from this interaction leads to the measurement result.
  • Measuring devices comprising a cell delimited by a membrane semi-permeable to a gas such as carbon dioxide contained in a medium to be studied and containing a colored solution reacting to the gas passing through the membrane.
  • the cells of these known devices are relatively large, which has the drawback of increasing the diffusion time of the medium to be studied through the membrane until it reacts with all of the colored indicator solution and therefore does not allow the dissolved gas in the colored indicator to rapidly balance with the gas dissolved in the medium to be studied. The measurements are therefore not completely representative of the gas concentration of the medium.
  • the device according to the invention overcomes these drawbacks.
  • a measuring cell with suitable colored indicator intended to be immersed in a medium characterized in that it comprises in combination a thin and hollow elongated element, a permeable or semi-permeable membrane sheathing the elongated element, a volume of colored indicator solution contained in the elongated element, the variations in color of which are indicative of the variations in said medium, the wall of said elongated element being provided with at least one opening over part of its length so as to obtain a surface of relatively large exchange between the volume of colored indicator solution and said medium through the membrane.
  • the section of the elongated element is preferably chosen to be substantially equal to that of said fibers so that the light passing from one to the other crosses substantially the entire volume of the colored indicator solution contained in the elongated element.
  • the elongated element is a cylindrical tube.
  • a cylindrical tube comprising openings distributed over a part of its periphery, the area of these openings being chosen so as to obtain a maximum value of the ratio Sr / Vr between the reaction surface and the volume of the colored indicator solution.
  • This ratio Sr / Vr will preferably be chosen greater than 2 / d where d is the diameter of the tube.
  • the diameter of the measuring cell will preferably be less than 1 mm, so as to minimize the time of diffusion of the medium through the membrane to the colored indicator solution.
  • the colored indicator solution may include thymol blue.
  • the membrane which is to sheath the elongated element can be a membrane produced by molding on a mold of a shape adapted to that of the elongated element .
  • the molding can be obtained by immersing the mold in a liquid bath containing a selected substance followed by solidification.
  • the liquid bath may contain an air-curable substance.
  • the elongated element can be polished.
  • the seal between the elongated element and each optical fiber can be obtained by heat shrinking a portion of sheath made of shrinkable material.
  • Operations b, c, and d can be carried out, the various elements being immersed in the colored indicator solution previously rid of any dissolved gas.
  • the colored indicator solution can be introduced into the elongated element before it is sheathed by said membrane.
  • the device also makes it possible to minimize, due to its geometry, the problems of fouling or marine soiling coming to be fixed on the membrane, which in fact is not planar.
  • Another advantage of the invention is to provide sealing without mechanical stress at the optical fiber.
  • the cell comprises an elongated hollow element open at its two opposite ends such as a tube, arranged to contain a colored indicator solution which is capable of reacting to certain variations of a medium to be studied and to allow this reaction.
  • a gas permeable membrane coats the tube with the exception of its two terminal openings.
  • the side wall of the tube has at least one opening allowing exchanges with the external medium through the membrane.
  • the cell according to the invention as it is shown in FIG. 1, is more particularly adapted to measure the content of carbon dioxide dissolved in a medium in which it is immersed.
  • the cell comprises a hollow elongate element such as a tube, arranged to contain a colored indicator solution which is capable of reacting to this variation in content and to allow this reaction.
  • the cell comprises a membrane 1 permeable or semi-permeable to reactive chemical species which sheaths an elongated element 2, such as a cylindrical tube, over its entire length with the exception of its longitudinal ends, the tube having on its wall at least an opening 3 which will allow the medium in which the cell is immersed to diffuse into the colored indicator solution.
  • Two optical fibers 4, 5 are connected respectively to the two opposite ends of the tube 2, the end of the fiber devoid of its sheath penetrating into the tube has a diameter substantially equal to the internal diameter of the tube so that the light coming from the optical fiber runs through the entire reaction volume Vr containing the colored indicator solution.
  • the reaction volume Vr delimited by the tube 2 and the ends of the fibers 4, 5 entering the tube contains a colored indicator 6 adapted to react as a function of variations in the gas content of the medium to be analyzed.
  • Two sleeves 7, 8 are placed around the end portions of the tube 2 so as to hold the membrane and each of the two fibers 4, 5 relative to the tube 2.
  • the sleeves 7, 8 seal the joint between each fibers and the tube.
  • the seals 7, 8 consist, for example, of a portion of heat-shrinkable sheath which makes it possible to seal between the sheathed tube and the optical fibers without inducing stresses in the optical fiber which would risk damaging it.
  • the membrane 1 can be made of any material allowing the rapid diffusion of a particular chemical species present in the medium to be analyzed in the whole of the colored indicator solution, itself contained in the reaction volume.
  • the membranes are, for example, silicone membranes manufactured in the laboratory from a polymer solution sold by the company Dow Corning under the number 92009.
  • membranes can also be made from a substance which is a function of the chemical species to be studied as will be seen later in the description of the method of manufacturing the cell.
  • the thickness of the membrane is chosen so as to have a rapid diffusion rate from the medium to be studied towards the reaction volume and at the same time to ensure a certain resistance to the membrane.
  • the thickness of this membrane is preferably less than 200 micrometers, so as to reduce the time for equilibrium of the colored indicator solution with the medium to be studied and thus to minimize the time interval between two measurements.
  • reaction surface Sr The sum of the surfaces of the openings distributed over the wall of the central cylindrical part of the tube defines a reaction surface Sr.
  • the lateral openings are enlarged as much as possible or their number is increased as much as possible so that the ratio of the exchange surface Sr with the medium to be studied, the reaction volume V2 is as high as possible.
  • the value of this ratio is preferably greater than 2 / d where d is the diameter of the tube.
  • a tube whose diameter value is as small as possible.
  • the value of this diameter will preferably be less than 1 mm.
  • an elongated element such as a tube 2 of small section which can be, for example stainless steel.
  • At least one opening 3 is drilled in the side wall of the central part of this tube.
  • the number of openings 3 and their arrangement are determined as a function of the value of the reaction surface which it is desired to obtain and of technological constraints.
  • the drilling of these openings 3 is done by electrochemistry, electroerosion, laser or any other method making it possible to produce small openings.
  • the cell can be assembled in several ways which will be given by way of illustration and not limitation.
  • the tube 2 is drilled over its entire length with the exception of its longitudinal ends with a prefabricated permeable or semi-permeable membrane 1.
  • the drilled tube sheathed with a colored indicator solution 6 is then filled, then an optical fiber 4, 5 is introduced at each of its longitudinal ends, each of them being pressed into the tube until its end is in the vicinity, without however obstructing it, openings 3 in the wall of the tube 2 to avoid any risk of reaction between the medium to be studied and the solution with colored indicator outside the reaction volume Vr.
  • a reaction could possibly take place in the space between the membrane 1 and the wall of the tube 2.
  • the optical fibers 4, 5, having been introduced into the tube 2, the seal between the tube, the sheath and the optical fiber using sleeves 7, 8, consisting, for example, of a heat-shrinkable sheath so that when heated it comes to match the external shape of the sheathed tube 2 and the optical fiber 4, 5 and thus ensuring a perfect seal.
  • a light source is then connected to the end of one of the optical fibers 4 and to the end of the second optical fiber 5 is a light receiver.
  • the manufacturing of the membrane is integrated into the manufacturing process of the cell.
  • a support having a shape corresponding to the final shape of the desired membrane is immersed in a bath containing a substance which is chosen according to the medium to be studied and which allows the desired chemical equilibration.
  • the material of this support is chosen so as to allow easy removal of the membrane.
  • a polymerizable monomer with oxygen from the air it is thus possible to use a polymerizable monomer with oxygen from the air.
  • the coated support is then removed from the substance and the substance is allowed to take a solid form.
  • the procedure is as follows: the tube having been pierced according to the method described above, the tube 2 and the membrane are immersed 1 in the colored indicator solution 6.
  • the colored indicator solution 6 is degassed and continuously maintained in a degassed state by any known means which may be stirring.
  • the tube 2 being immersed in the colored indicator solution 6, it fills with the latter.
  • the tube 2 is then sheathed with the membrane 1, this operation always being carried out in the colored indicator solution.
  • the end of two optical fibers 4, 5 is then immersed enough to be able to introduce them into each end of the sheathed tube.
  • the optical fibers 4, 5 are introduced into the tube until their end is placed in the vicinity of the opening 3 without however obstructing it, then the sealing sleeves 7, 8 are put in place before to connect the fibers to the light source and the light receiver.
  • This embodiment is particularly suitable for the manufacture of a cell intended for analyzing media containing ions sensitive to the presence of gas, since all the mounting operations are carried out in the degassed colored indicator solution is maintained in a degassed state.
  • the colored indicator solution comprises thymol blue dissolved in NaCl and NaHCO 3, this solution being kept degassed during the cell manufacturing process.
  • the sheathing operation of the tube can be done in several ways. During this operation, it is possible to remove the support having served to manufacture the membrane, the support then serving as a guide for the tube which it is sought to sheath. This support may also have been removed prior to the sheathing operation.
  • the cell described in FIG. 1 can be used in the following way: the cell is immersed in the medium to be studied, the content of which is to be determined in the form of carbon dioxide dissolved in the form of carbon dioxide or combined in the form of carbonates and bicarbonates.
  • the light having completely swept through the reaction volume is received by the receiving fiber 5 placed at the other end of the tube 1 and analyzed by means of an appropriate photodetector.
  • the intensity of the light is a function of the carbon dioxide content contained in the medium studied and therefore, as a result of the establishment of a carbon equilibrium, of the pH of the indicator solution colored by colorimetry, as is well known. of the skilled person.
  • the measurement could be carried out by methods such as fluorescence methods or by Raman spectrometry.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
EP93400962A 1992-04-14 1993-04-13 Sonde de mesure à membrane à perméabilite sélective et son procédé de fabrication Withdrawn EP0566480A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9204552A FR2689977B1 (fr) 1992-04-14 1992-04-14 Cellule de mesure a membrane a permeabilite selective et son procede de fabrication.
FR9204552 1992-04-14

Publications (1)

Publication Number Publication Date
EP0566480A1 true EP0566480A1 (fr) 1993-10-20

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ID=9428837

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Application Number Title Priority Date Filing Date
EP93400962A Withdrawn EP0566480A1 (fr) 1992-04-14 1993-04-13 Sonde de mesure à membrane à perméabilite sélective et son procédé de fabrication

Country Status (4)

Country Link
EP (1) EP0566480A1 (no)
CA (1) CA2093990A1 (no)
FR (1) FR2689977B1 (no)
NO (1) NO931381L (no)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009015723A1 (de) * 2007-07-05 2009-02-05 Ses-Entwicklung Gmbh Stoffkonzentrations-sensor und herstellverfahren dafür

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073558A2 (en) * 1981-08-25 1983-03-09 THE UNITED STATES OF AMERICA as represented by the Secretary United States Department of Commerce Fiber optic pH probe for tissue measurements
EP0279004A1 (en) * 1987-02-17 1988-08-24 Hewlett-Packard GmbH Method for manufacturing a measuring probe
WO1991015867A1 (en) * 1990-03-30 1991-10-17 Fiberchem, Inc. Reservoir fiber optic chemical sensors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073558A2 (en) * 1981-08-25 1983-03-09 THE UNITED STATES OF AMERICA as represented by the Secretary United States Department of Commerce Fiber optic pH probe for tissue measurements
EP0279004A1 (en) * 1987-02-17 1988-08-24 Hewlett-Packard GmbH Method for manufacturing a measuring probe
WO1991015867A1 (en) * 1990-03-30 1991-10-17 Fiberchem, Inc. Reservoir fiber optic chemical sensors

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
APPLIED SPECTROSCOPY vol. 44, no. 1, Janvier 1990, BALTIMORE US pages 128 - 132 T. VO-DINH ET AL 'Phase-resolved fiber-optics fluoroimmunosensor' *
SPIE MICRO-OPTICS (1988) vol. 1014, pages 73 - 76 M. BACCI ET AL 'A compact optical fibre device for the detection of pH' *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009015723A1 (de) * 2007-07-05 2009-02-05 Ses-Entwicklung Gmbh Stoffkonzentrations-sensor und herstellverfahren dafür
US8213013B2 (en) 2007-07-05 2012-07-03 Ses-Entwicklung Gmbh Substance concentration sensor and production method therefor

Also Published As

Publication number Publication date
CA2093990A1 (fr) 1993-10-15
FR2689977A1 (fr) 1993-10-15
NO931381L (no) 1993-10-15
FR2689977B1 (fr) 1997-01-24
NO931381D0 (no) 1993-04-14

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